journal article·2024-02-02Open access

Hydrophobic and Photocatalytic Treatment for the Conservation of Painted Lecce stone in Outdoor Conditions: A New Cleaning Approach

Laura Bergamonti, Marianna Potenza, Federica Scigliuzzo, Sandro Meli, Antonella Casoli, Pier Paolo Lottici, Claudia Graiff

Applied Sciences· Volume 14· Issue 3

Abstract

Self-cleaning and hydrophobic treatments based on TiO2 and SiO2 nanoparticles are widely applied for the preservation of cultural heritage materials, to improve their resilience in polluted environments. Excellent results have been obtained on stone materials, but experiments on painted stone surfaces, such as wall paintings and polychrome plasters used in historic buildings, are still limited. In this work, we present a study on the use of water dispersions of TiO2 nanoparticles obtained via sol-gel and organically modified silica (OrMoSil) for cleaning and protective purposes on Lecce stone, a carbonate stone, widely used for its excellent workability but easily attacked by atmospheric agents and pollutants. First, we evaluated the harmlessness of the treatment on Lecce stone through colorimetric tests, water absorption by capillarity and permeability to water vapor. The photocatalytic activity of the TiO2 nanoparticles was assessed by photo-degradation of methyl orange and methylene blue dyes. The dispersion was then applied on painted samples prepared according to ancient recipes to confirm the effectiveness of the cleaning. The proposed TiO2/OrMoSil-based coating can act as a self-cleaning and protective treatment on lithic surfaces to prevent degradation phenomena and preserve the original appearance of the monument.
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Research context

OpenAlex topics: Building materials and conservation · Conservation Techniques and Studies · Cultural Heritage Materials Analysis

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Department of Chemistry, Life Sciences and Environmental Sustainability, University of Parma, Parco Area delle Scienze 17a, 43124 Parma, Italy

Department of Mathematical, Physical and Computer Sciences, University of Parma, Parco Area delle Scienze 7a, 43124 Parma, Italy

Funding

NextGenerationEU—Italian Ministry of University and Research

References (94)

Show source-provided references
1. Basso, E., Carò, F., and Abramitis, D.H. (2023). Polychromy in Ancient Greek Sculpture: New Scientific Research on an Attic Funerary Stele at the Metropolitan Museum of Art. Appl. Sci., 13.10.3390/app13053102 ↗
2. Painting in Stone: Architecture and the Poetics of Marble from Antiquity to the Enlightenment, by Fabio Barry10.1080/00043079.2022.2066929 ↗
3. “Precious colours” in Ancient Greek polychromy and painting: Material aspects and symbolic values
4. Kreijn, L., Ryan, G., Rivenc, R., Tajiri, R.V., Chin, Z., Wolfe, J., Kenshe, S., and Breder, F. (2013, January 4–5). Conserving Outdoor Painted Sculpture. Proceedings of the Interim Meeting of the Modern Materials and Contemporary Art Working Group of ICOM-CC, Kröller-Müller Museum, Otterlo, The Netherlands.
5. The importance of colour on ancient marble sculpture10.1111/j.1467-8365.2009.00666.x ↗
6. Fassina, V. (1994). General criteria for the cleaning of stone: Theoretical aspects and methodology of application. In Stone Material in Monuments: Diagnosis and Conservation, Scuola Universitaria CUM Conservazione dei Monumenti.
7. Chromatic alterations induced by preservation treatments on paper: The case of Ag-functionalized nanocrystalline cellulose10.1016/j.culher.2023.09.008 ↗
8. (2021). Conservation of Cultural Heritage—Procedure for the Analytical Evaluation to Select Cleaning Methods for Porous Inorganic Materials used in Cultural Heritage (Standard No. EN 17488:2021).
9. (2014). Conservation of Cultural Heritage—Surface Protection for Porous Inorganic Materials—Laboratory Test Methods for the Evaluation of the Performance of Water Repellent Products (Standard No. EN 16581:2014).
10. Conservation strategies against graffiti vandalism on Cultural Heritage stones: Protective coatings and cleaning methods10.1016/j.porgcoat.2017.08.010 ↗
11. Soiling of building stones in urban environments10.1016/S0360-1323(02)00017-3 ↗
12. Chemical and colorimetric analysis for the characterization of degradation forms and surface colour modification of building stone materials10.1016/j.conbuildmat.2021.124356 ↗
13. Science, value and material decay in the conservation of historic environments10.1016/j.culher.2016.03.007 ↗
14. Quantitative data on carbon fractions in interpretation of black crusts and soiling on European built heritage10.1016/j.atmosenv.2005.01.040 ↗
15. Effect of long-term changes in air pollution and climate on the decay and blackening of European stone buildings10.1144/GSL.SP.2007.271.01.13 ↗
16. Efficiency assessment of hybrid coatings for natural building stones: Advanced and multi-scale laboratory investigation10.1016/j.conbuildmat.2018.05.289 ↗
17. Water-repellent properties of fluoroelastomers on a very porous stone: Effect of the application procedure10.1016/j.porgcoat.2012.11.005 ↗
18. The measurement of surface roughness to determine the suitability of different methods for stone cleaning10.1088/1742-2132/9/4/S108 ↗
19. New cleaning strategies based on carbon nanomaterials applied to the deteriorated marble surfaces: A comparative study with enzyme based treatments10.1016/j.apsusc.2012.01.076 ↗
20. A review of health hazards linked to the use of lasers for stone cleaning10.1016/S1296-2074(02)01224-4 ↗
21. Baer, N.S., Sabbioni, S., and Sors, A.I. (1991). Science, Technology, and European Cultural Heritage, Butterworth-Heinemann.
22. Doehne, E., and Price, C.A. (2010). Stone Conservation: An Overview of Current Research, Getty Conservation Institute. [2nd ed.].
23. Measuring weathering and nanoparticle coating impact on surface roughness of natural stones10.1080/00393630.2018.1507706 ↗
24. Bergamonti, L., Graiff, C., Simeti, S., and Casoli, A. (2023). The 20th Century Wall Paintings in the Chapel of the Fallen in Parma Cathedral (Italy): Scientific Investigations for a Correct Conservation. Project. Appl. Sci., 13.10.3390/app13127235 ↗
25. A multi-analytical a pproach for the characterization of wall painting materials on contemporary buildings10.1016/j.saa.2016.08.017 ↗
26. Advances in characterization of colourful residues unearthed in Persepolis West craft zone using microscopic and spectroscopic techniques10.1016/j.microc.2021.106304 ↗
27. Development of integrated innovative techniques for paintings examination: The case studies of The Resurrection of Christ attributed to Andrea Mantegna and the Crucifixion of Viterbo attributed to Michelangelo’s workshop10.1016/j.culher.2019.05.005 ↗
28. Colantonio, C., Lanteri, L., Bocci, R., Valentini, V., and Pelosi, C. (2023). “A Woman Clothed with the Sun”: The Diagnostic Study and Testing of Enzyme-Based Green Products for the Restoration of an Early 17th Century Wall Painting in the Palazzo Gallo in Bagnaia (Italy). Appl. Sci., 13.10.20944/preprints202311.0837.v1 ↗
29. Obtaining SiO2-fluorinated PLA bionanocomposites with application as reversible and highly-hydrophobic coatings of buildings10.1016/j.porgcoat.2015.09.024 ↗
30. TiO2–SiO2–PDMS nano-composite hydrophobic coating with self-cleaning properties for marble protection10.1016/j.porgcoat.2012.10.006 ↗
31. Mosquera, M.J., Pinho, L., Facio, D.S., and Elhaddad, F. (2014). Science, Technology and Cultural Heritage, Proceedings of the 2nd International Congress on Science and Technology for the Conservation of Cultural Heritage, Sevilla, Spain, 24–27 June 2014, CRC Press.
32. Producing photoactive, transparent and hydrophobic SiO2-crystalline TiO2 nanocomposites at ambient conditions with application as self-cleaning coatings10.1016/j.apcatb.2014.03.042 ↗
33. A review in using agar gels for cleaning art surfaces10.1016/j.culher.2020.01.008 ↗
34. Enzymes as tools for conservation of works of art10.1016/j.culher.2021.06.005 ↗
35. Ortega-Morales, B.O., and Gaylarde, C.C. (2021). Bioconservation of historic stone buildings—An updated review. Appl. Sci., 11.10.3390/app11125695 ↗
36. Baglioni, P., Chelazzi, D., and Giorgi, R. (2015). Nanotechnologies in the Conservation of Cultural Heritage, Springer.10.1007/978-94-017-9303-2 ↗
37. Laser cleaning in conservation of stone, metal, and painted artifacts: State of the art and new insights on the use of the Nd: YAG lasers10.1007/s00339-011-6690-8 ↗
38. Assessing the value of green conservation for cultural heritage: Positive and critical aspects of already available methodologies
39. The environmental impact of cleaning materials and technologies in heritage buildings conservation10.1016/j.enbuild.2018.01.051 ↗
40. Di Turo, F., and Medeghini, L. (2021). How green possibilities can help in a future sustainable conservation of cultural heritage in Europe. Sustainability, 13.10.3390/su13073609 ↗
41. Evaluation of the Photocatalytic Activity of Water-Based TiO2 Nanoparticle Dispersions Applied on Historical Painting Surfaces10.3390/heritage4030104 ↗
42. Smart cleaning of cultural heritage: A new challenge for soft nanoscience10.1039/C1NR10911A ↗
43. David, M.E., Ion, R.M., Grigorescu, R.M., Iancu, L., and Andrei, E.R. (2020). Nanomaterials used in conservation and restoration of cultural heritage: An up-to-date overview. Materials, 13.10.3390/ma13092064 ↗
44. Lazzara, G., and Fakhrulli, R.F. (2018). Nanotechnologies and Nanomaterials for Diagnostic, Conservation and Restoration of Cultural Heritage, Elsevier.
45. Biocleaning of Cultural Heritage stone surfaces and frescoes: Which delivery system can be the most appropriate?10.1007/s13213-014-0938-4 ↗
46. D’Amico, S., and Venuti, V. (2022). Handbook of Cultural Heritage Analysis, Springer.10.1007/978-3-030-60016-7 ↗
47. Application of a new photocatalytic nanomaterial obtained by Pulse Laser Ablation for Polychrome Paintings Conservation: A feasibility study
48. Analysis of the distribution of titanium oxide nanoparticles on paintings10.1088/1742-6596/2204/1/012070 ↗
49. Gherardi, F., Roveri, M., Goidanich, S., and Toniolo, L. (2018). Photocatalytic nanocomposites for the protection of European architectural heritage. Materials, 11.10.3390/ma11010065 ↗
50. Compatibility of photocatalytic TiO2-based finishing for renders in architectural restoration: A preliminary study10.1016/j.buildenv.2014.05.027 ↗
51. Novel multifunctional coatings with photocatalytic and hydrophobic properties for the preservation of the stone building heritage10.1016/j.conbuildmat.2015.05.100 ↗
52. Recent advances in photocatalytic self-cleaning performances of TiO2-based building materials10.1039/D2RA07839B ↗
53. Potentials and limits of oxidative photocatalysisand possible applications in the field of cultural heritage
54. D’Amico, S., and Venuti, V. (2022). Handbook of Cultural Heritage Analysis, Springer International Publishing.10.1007/978-3-030-60016-7 ↗
55. Hosseini, M., and Karapanagiotis, I. (2018). Advanced Materials for the Conservation of Stone, Springer.10.1007/978-3-319-72260-3 ↗
56. Photocatalytic degradation of methyl orange using polymer–titania microcomposites10.1016/j.jcis.2009.02.016 ↗
57. Titanium Dioxide Photocatalysis in Atmospheric Chemistry10.1021/cr3002092 ↗
58. Use of TiO2 in photocatalysis for air purification and wastewater treatment: A review10.30684/etj.2021.131177.1015 ↗
59. Photocatalytic degradation of organic pollutants using TiO2-based photocatalysts: A review10.1016/j.jclepro.2020.121725 ↗
60. Photocatalytic activity improvement and application of UV-TiO2 photocatalysis in textile wastewater treatment: A review10.1016/j.jece.2019.103248 ↗
61. TiO2 based Photocatalysis membranes: An efficient strategy for pharmaceutical mineralization10.1016/j.scitotenv.2022.157221 ↗
62. Bergamonti, L., Graiff, C., Bergonzi, C., Potenza, M., Reverberi, C., Ossiprandi, M.C., Lottici, P.P., Bettini, R., and Elviri, L. (2022). Photodegradation of Pharmaceutical Pollutants: New Photocatalytic Systems Based on 3D Printed Scaffold-Supported Ag/TiO2 Nanocomposite. Catalysts, 12.10.3390/catal12060580 ↗
63. Photocatalytic N-doped TiO2 for self-cleaning of limestones10.1140/epjp/i2019-12981-6 ↗
64. A novel TiO2–SiO2 nanocomposite converts a very friable stone into a self-cleaning building material10.1016/j.apsusc.2012.10.142 ↗
65. Self-cleaning durability assessment of TiO2/SiO2 photocatalysts coated concrete: Effect of indoor and outdoor conditions on the photocatalytic activity10.1016/j.buildenv.2021.108743 ↗
66. Au-TiO2/SiO2 photocatalysts for building materials: Self-cleaning and de-polluting performance10.1016/j.buildenv.2019.106347 ↗
67. Ham, W.E. (1962). Classification of Carbonate Rocks—A Symposium, American Association of Petroleum Geologists Mem.10.1306/M1357 ↗
68. The Flight of Saint Mary Magdalene—A Case Study of the Dismantling, Repositioning and Restoration of a Votive Aedicule and Wall Painting in Nardò, Lecce, Italy10.3390/heritage6040182 ↗
69. Esposito, D., Vitarelli, F., Vita, L., and D’Onofrio, M. (2017). RPR, Rilievo, Progetto, Riuso, Maggioli.
70. De Pascalis, D.G., Leucci, G., De Giorgi, L., Giuri, F., and Scardozzi, G. (2019, January 4–6). The Basilica of Santa Caterina d’Alessandria in Galatina (Lecce, Italy): NDT surveys for the conservation project. Proceedings of the 2019 IMEKO TC-4 International Conference on Metrology for Archaeology and Cultural Heritage, Florence, Italy.
71. Gryparis, C., Krasoudaki, T., and Maravelaki, P.N. (2022). Self-Cleaning Coatings for the Protection of Cementitious Materials: The Effect of Carbon Dot Content on the Enhancement of Catalytic Activity of TiO2. Coatings, 12.10.3390/coatings12050587 ↗
72. Effective photocatalytic decolorization of methyl orange utilizing TiO2/ZnO/chitosan nanocomposite films under simulated solar irradiation10.1016/j.desal.2011.10.036 ↗
73. Degradation of methylene blue and methyl orange by palladium-doped TiO2 photocatalysis for water reuse: Efficiency and degradation pathways10.1016/j.jclepro.2018.08.110 ↗
74. Photocatalytic activities of TiO2 layers immobilized on glass substrates by dip-coating technique toward the decolorization of methyl orange as a model organic pollutant10.1016/j.jece.2017.02.025 ↗
75. Edwards, H.G.M., Vandenabeele, P., and Colomban, P. (2023). Raman Spectroscopy in Cultural Heritage Preservation, Springer.10.1007/978-3-031-14379-3 ↗
76. Pigments—Iron-based red, yellow, and brown ochres10.1007/s12520-021-01482-2 ↗
77. (2001). Conservation of Cultural Property—Test Methods—Natural and Artificial Stone Materials—Hydrophobic Products (Standard No. UNI 10921:2001).
78. Preliminary Studies of the Effects of Nanoconsolidants on Mural Paint Layers with a Lack of Cohesion10.3390/heritage4040183 ↗
79. Microscopic analysis of wall painting techniques: Laboratory replicas and romanesque case studies in Southern Switzerland10.1080/00393630.2017.1422891 ↗
80. (2010). Conservation of Cultural Property—Test Methods—Color Measurement of Surfaces (Standard No. UNI EN 15886:2010).
81. (2010). Conservation of Cultural Property—Test Methods—Determination of Water Absorption by Capillarity (Standard No. UNI EN 15801:2010).
82. The dynamics of capillary flow10.1103/PhysRev.17.273 ↗
83. Superhydrophobic films for the protection of outdoor cultural heritage assets10.1007/s00339-009-5233-z ↗
84. (2010). Conservation of Cultural Property—Test Methods—Determination of Static Contact Angle (Standard No. UNI EN 15802: 2010).
85. Weathering resistance of PMMA/SiO2/ZrO2 hybrid coatings for sandstone conservation10.1016/j.polymdegradstab.2017.12.012 ↗
86. (2001). Conservation of Cultural Property—Natural Stone Test Method—Determination of Resistance to Salt Crystallization (Standard No. UNI EN 12370:2001).
87. Ohta, N., and Robertson, A.R. (2005). Colorimetry: Fundamentals and Applications, John Wiley & Sons, Ltd.. Chapter 5.10.1002/0470094745 ↗
88. Biostratigraphy and chronostratigraphy of the Miocene Pietra Leccese in the type area of Lecce (Apulia, southern Italy)
89. Non-destructive techniques to assess mechanical and physical properties of soft calcarenitic stones10.1016/j.proche.2013.03.006 ↗
90. Raman line shapes of optical phonons of different symmetries in anatase TiO2 nanocrystals10.1021/jp9046193 ↗
91. Phonon confinement effects in the Raman scattering by TiO2 nanocrystals10.1063/1.120648 ↗
92. Evaluation of uniform color spaces developed after the adoption of CIELAB and CIELUV10.1111/j.1520-6378.1994.tb00070.x ↗
93. Titania-silica nanocomposite photocatalysts with application in stone self-cleaning10.1021/jp2074623 ↗
94. Water repellent ORMOSIL films for the protection of stone and other materials10.1016/j.matlet.2014.05.163 ↗